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  • kinetics  (355)
  • Springer  (355)
  • Cambridge University Press
  • 1995-1999  (286)
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  • 1
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 261 (1983), S. 188-189 
    ISSN: 1435-1536
    Schlagwort(e): Polymerization ; kinetics ; redox polymerization ; acrylamide
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Materialart: Digitale Medien
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  • 2
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 262 (1984), S. 366-373 
    ISSN: 1435-1536
    Schlagwort(e): kinetics ; isothermal crystallization ; polymer ; spherulite ; differential scanning calorimetry
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract In the DSC technique, isothermal crystallization experiments are usually performed on thin flat specimens, but their interpretation generally uses theories developed for an unbounded volume. In this paper, isothermal crystallization of spherical entities in the volume limited by two parallel infinite planes is considered. Our model, derived from Avrami's theory, gives an analytical expression for the transformed volume fraction as a function of time. It is shown that the influence of thickness becomes important when thickness becomes of the order of or smaller than the average spherulite radius. The main effects of a decreasing thickness are a slower crystallization kinetics and a decrease in the Avrami exponent. These results can be used to interpret experimental data obtained in isothermal polymer crystallization.
    Materialart: Digitale Medien
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  • 3
    Digitale Medien
    Digitale Medien
    Springer
    Colloid & polymer science 261 (1983), S. 621-625 
    ISSN: 1435-1536
    Schlagwort(e): Polyamide 6 ; crystallisation ; kinetics ; titania
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Maschinenbau
    Notizen: Abstract The kinetics of isothermal and nonisothermal crystallization of polyamide-6 (PA6) containing titania was studied by means of DSC. It was found thatTiO 2 causes an acceleration in the crystallization of polyamide-6 and lowers the value of the Avrami exponent,n. The presence of TiO2 does not affect equilibrium melting pointT m 0 , glass temperatureT g, or surface free energiesσ e andσ of the basal and lateral surfaces.
    Materialart: Digitale Medien
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  • 4
    Digitale Medien
    Digitale Medien
    Springer
    Fire technology 20 (1984), S. 47-63 
    ISSN: 1572-8099
    Schlagwort(e): Extinguishment ; fire modeling ; mass loss ; heat release ; char ; reflash ; sprinklers ; radiant flux ; kinetics ; reaction rate ; heat loss ; ash ; latent heat ; spray density ; extinguishing agents
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Architektur, Bauingenieurwesen, Vermessung
    Notizen: Abstract The Ad Hoc Mathematical Fire Modeling Working Group was organized about seven years ago to facilitate voluntary cooperation and coordination in developing mathematical fire modeling capability. The group has a steering committee of representatives of agencies that support fire modeling and related research. These include the National Bureau of Standards' Center for Fire Research, Factory Mutual Research Corp., the Naval Research Laboratory, NASA, and the Federal Aviation Agency. The Group holds plenary meetings when it seems desirable to do so (about once each 1 1/2 years), and workshops on topical subjects. Three workshops were held in 1983. Normally, Group meetings are held before or after other meetings at which a number of interested personnel would likely be present. Minutes are mailed to those who attended and to others (including European and Japanese personnel) who have indicated interest. This workshop was arranged by Ron Alpert of Factory Mutual Research Corp. and held at their facilities at Norwood, MA, in November 1983.
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  • 5
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 11 (1982), S. 339-346 
    ISSN: 1572-8927
    Schlagwort(e): Carbon dioxide ; hydrolysis ; aqueous solution ; kinetics ; activation volume
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The pressure dependence of the dehydration reaction of H2CO3 was measured in acidic aqueous solution for pressures up to 1 kbar using a high-pressure stopped-flow instrument. The corresponding volume of activation was found to be 6.4±0.4 cm3-mol−1 at 25°C and 0.5 ionic strength. Volume equation calculations result in a value of −9.9±1.9cm3-mol−1 for the volume of activation for the hydrolysis of CO2 under the same conditions. For the first time, the reaction mechanism can be interpreted in terms of dissociative and associative modes, respectively. These data are used to construct an overall reaction volume profile.
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  • 6
    ISSN: 1572-8927
    Schlagwort(e): Temperature jump ; kinetics ; thermodynamics ; TRIS ; iminodiacetic acid ; magnesium ion ; phenol red
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Equations describing the temperature jump amplitudes associated with a system of two coupled reactions (TRIS-phenol red) as well as the ternary system (Mg2+-iminodiacetic acid-phenol red) are presented. The termodynamic parameters calculated from experimentally measured temperature perturbation amplitudes using a multiparametric curve fitting procedure are found to be in good agreement with those determined from pH- and costant rate thermometric titrations. For phenol red, pK I =7.55, ΔH I =3.45 kcal, and for Mg2+ iminodiacetic acid, log K M =2.84, ΔH M =3.25 kcal, were obtained. It is shown that this method can be used to determine accurate thermodynamic enthalpy changes over a narrow temperature interval of less than 1.0°C from a single experiment requiring about 50 μl of sample solution.
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  • 7
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 12 (1983), S. 771-781 
    ISSN: 1572-8927
    Schlagwort(e): Ultrasonics ; kinetics ; aqueous solution ; iso-butyl cellosolve
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Ultrasonic absorption and velocity measurements in aqueous solution of iso-butyl cellosolve (ethylene glycol iso-butyl ether) as a function of the concentration are reported. The two relaxational absorptions have been attributed to the perturbation of the equilibria expressed by AB⇌A+B and Aα(1/n)An where A is the solute, B is the solvent, AB is the complex and A n is the solute aggregate. The rate constants for each step have been determined. From the concentration dependence of the maximum excess absorption per wave length, the enthalpy change and the volume change for the reaction between the solute and the solvent have been determined for aqueous solutions of butyl cellosolve (ethylene glycol n-butyl ether), iso-butyl cellosolve and propyl cellosolve (ethylene glycol n-propyl ether). The results are consistent with a hydrogen bonding reaction. The effect of the ethers on water structure are considered and it is clear that the fraction of water molecules which can hydrogen bond to the solute decreases with the increasing hydrophobicity of the solute.
    Materialart: Digitale Medien
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  • 8
    Digitale Medien
    Digitale Medien
    Springer
    Journal of applied electrochemistry 29 (1999), S. 191-200 
    ISSN: 1572-8838
    Schlagwort(e): cyclic redox reaction ; dissolution ; kinetics ; manganese dioxide ; mechanism ; pyrite
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Elektrotechnik, Elektronik, Nachrichtentechnik
    Notizen: Abstract This paper describes a study of the kinetics and mechanism of MnO2 dissolution in H2SO4 in the presence of pyrite through leaching and electrochemical parameters. Manganese(iv) was found to dissolve mainly through reduction by the ferrous ion generated during oxidation of pyrite by the ferric ion. The oxidation which is slower and rate controlling may proceed through two different reactions, one producing S0 and the other SO42−. Manganese dissolution runs at the same rate as that of pyrite oxidation by maintaining ferrous ion concentration at a much lower level than that of ferric. Kinetic equations based on corrosion coupling principles are developed to explain the observed leaching behaviour.
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  • 9
    Digitale Medien
    Digitale Medien
    Springer
    Journal of chemical crystallography 28 (1998), S. 69-72 
    ISSN: 1572-8854
    Schlagwort(e): Co(III) complex ; crystal structure ; kinetics ; steric effects
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Geologie und Paläontologie , Physik
    Notizen: Abstract The title compound crystallizes in the orthorhombic space group Pnma, with a = 7.9209(5), b = 9.818(1), c = 16.867(2) Å, and Z = 4. The structure was solved employing 1864 independent x-ray reflections with I〉2σ(I) by Patterson and difference Fourier techniques and refined by full-matrix least-squares to R = 0.036. The trans-[CO(NH3)4(NH2CH3)Cl](ClO4)2 molecule is on a crystallographic mirror plane. The cobalt ion is in an elongated octahedral coordination with four equatorial ammonia ligands [average Co–N distance equal to 1.966(2) Å], an axial methylamine [Co–N=1.965(3)Å], and an axial chlorine ion [Co–Cl=2.2771(9)Å]. Kinetic steric effects of the complex are interpreted in terms of structural results.
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  • 10
    Digitale Medien
    Digitale Medien
    Springer
    Adsorption 1 (1995), S. 133-151 
    ISSN: 1572-8757
    Schlagwort(e): PSA process ; sensitivity ; equilibria ; kinetics ; heats
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Physik , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract Mathematical models for pressure swing adsorption (PSA) processes essentially require the simultaneous solutions of mass, heat and momentum balance equations for each step of the process using appropriate boundary conditions for the steps. The key model input variables needed for estimating the separation performance of the process are the multicomponent adsorption equilibria, kinetics and heats of adsorption for the system of interest. A very detailed model of an adiabatic Skarstrom PSA cycle for production of high purity methane from a ethylene-methane bulk mixture is developed to study the sensitivity of the process performance to the input variables. The adsorption equilibria are described by the heterogeneous Toth model which accounts for variations of isosteric heats of adsorption of the components with adsorbate loading. A linear driving force model is used to describe the kinetics. The study shows that small errors in the heats of adsorption of the components can severely alter the overall performance of the process (methane recovery and productivity). The adsorptive mass transfer coefficients of the components also must be known fairly accurately in order to obtain precise separation performance.
    Materialart: Digitale Medien
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  • 11
    Digitale Medien
    Digitale Medien
    Springer
    Adsorption 2 (1996), S. 265-277 
    ISSN: 1572-8757
    Schlagwort(e): frequency response ; diffusion cell ; kinetics ; diffusion ; heat effects
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Physik , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract This paper deals with frequency response (FR) analysis of a closed diffusion cell system with two resonators, that is both the LHS and RHS volumes are modulated. The analysis is made for a homogeneous particle described by a single effective diffusivity as well as a biporous pellet described by macropore and micropore diffusions. It is shown that if the perturbation of the volume of the reservoir #2 is lagged behind that of the reservoir #1 by 3π/2, the pressure response in reservoir #1 is significantly enhanced with larger amplitude as well as phase angle. When the perturbations of the two reservoirs are out of phase, the heat effect is reduced and can become insignificant when the two perturbations are completely out of phase (ψ = π). Under such a condition, the pressure difference between the two reservoirs could be doubled. In the case of biporous pellets, it is shown that the FR behaviours obtained for micropore diffusion control and macropore diffusion control are well distinguished. In the former case, the FR system reduces to a traditional batch adsorber one while in the latter case, the FR behaviour is the same as for a two resonator system with homogeneous particles. This difference can be used for the discrimination of micropore and macropore diffusion processes.
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  • 12
    Digitale Medien
    Digitale Medien
    Springer
    Adsorption 3 (1997), S. 267-275 
    ISSN: 1572-8757
    Schlagwort(e): characterisation ; equilibria ; kinetics ; micropore size distribution ; n-butane ; nutshell
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Physik , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract Adsorption equilibria and dynamics ofn-butane on two activated carbon samples prepared from the physical activation of nutshell are studied in this paper. The micropore size distribution (MPSD) is considered as the main source of solid heterogeneity. Lennard-Jones' potential theory and Dubinin's theory (TVFM) are used in the equilibria data to derive the MPSD, which is well fitted by a Gamma distribution function. The adsorption energy distribution derived from the MPSD is very asymmetric for both the samples studied, and this energy distribution used in the HMSD/HMSMD kinetics models for the study of adsorption dynamics ofn-butane.
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  • 13
    Digitale Medien
    Digitale Medien
    Springer
    BioMetals 12 (1999), S. 1-10 
    ISSN: 1572-8773
    Schlagwort(e): acidophilic ; strain ; oxidation ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Recovery of metal values from sulfide ores by use of acidophilic microorganisms is gaining importance. A number of commercial/pilot plants are setup to find out the techno-economic feasibility of the overall process. The main drawback in the process is the slow kinetics of dissolution of metal values from the sulfide ores. To make the technology e attractive the kinetics should be improved considerably. There are various factors which determine the overall kinetics such as bacterial activity and concentration, iron and sulfur oxidation, oxygen consumption, reactor design and nature of ore. A brief review has been made dealing with the above parameters
    Materialart: Digitale Medien
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  • 14
    Digitale Medien
    Digitale Medien
    Springer
    Catalysis letters 37 (1996), S. 167-172 
    ISSN: 1572-879X
    Schlagwort(e): dissociation ; kinetics ; Co-Mo sulphide ; H2S
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract In this study, a high surface area 4Co∶6Mo∶100γ-Al2O3 sulphide prepared using precipitation from homogeneous solution (PFHS) has been used for the catalytic splitting of hydrogen sulphide into H2 and elemental sulphur. The activity of this new formulation was significantly better than previously reported recipes. Kinetic data collected over a wide range of H2S partial pressures between 883 and 983 K revealed that, although the decomposition followed a first-order law, a mechanism involving H2S adsorption on co-ordinative unsaturation sites of the Co-Mo sulphide catalyst gave a Langmuir-Hinshelwood rate expression that yielded satisfactory model parameters. In particular, the scission of the surface H-S bond appeared to be the rate determining step.
    Materialart: Digitale Medien
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  • 15
    Digitale Medien
    Digitale Medien
    Springer
    Catalysis letters 37 (1996), S. 173-179 
    ISSN: 1572-879X
    Schlagwort(e): ammonia synthesis ; iron catalysts ; potassium promotion ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Measurements were performed of reaction rate in the process of ammonia synthesis (T=370–470°C) on doubly promoted (DP) (Al2O3, CaO) and triply promoted (TP) (K2O, Al2O3, CaO) iron catalysts. The latter were obtained by impregnation of the reduced and subsequently passivated DP precursors with alcoholic solution of KOH. The studies were carried out under high total pressure (10 MPa) in a wide range of ammonia partial pressure in the gas phase: from 0.25 to about 7 bar. The results are shown to be authoritative for the so-called kinetic regime. The effect of the presence of K+ cations in the catalyst was the stronger, as the temperature of the reaction was the lower and, in particular, the ammonia pressure in the gas phase the higher. The obtained results are in good accordance with the results of Somorjai's studies on activity of iron single crystal surfaces both clean and covered with (K+O) adlayer.
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  • 16
    ISSN: 1572-882X
    Schlagwort(e): accelerated tests ; aging tests ; cellulose degradation ; durability ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract Accelerated aging tests are credible and useful to predict paper permanence only if such tests can be shown to correlate with natural aging. In the first part of this study, a kinetic model was developed based on the accelerated aging results. In this report, we have shown that this kinetic model can indeed predict the natural aging results of lignin-free sheets with a statistical confidence. This is the first quantitative comparison of accelerated aging with natural aging.
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  • 17
    Digitale Medien
    Digitale Medien
    Springer
    Journal of solution chemistry 27 (1998), S. 1123-1138 
    ISSN: 1572-8927
    Schlagwort(e): Sol–gel processing ; hydrolysis ; condensation ; kinetics ; methoxydimethyloctylsilane ; copper nitrate hydrate ; phase diagram
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The reaction rate was determined for copper nitrate hydrate with methoxydimethyloctylsilane (MDOS) in methanol. The rate constants of hydrolysis and condensation were established by quantitative measurement of the product and Karl Fischer water determination. The reaction with the hydrated copper salt resulted in the phase separation of an insoluble product from the reaction mixture. The structure of the product was determined, by Fourier Transform Infrared Spectrometry (FTIR) and Nuclear Magnetic Resonance (NMR) to be a dimer of the MDOS. The results showed the alcohol, producing condensation reaction was negligible in the formation of the dimer. contrary to the case for the well-known reaction by trialkoxysilanes and tetraalkoxysilanes.
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  • 18
    ISSN: 1572-8927
    Schlagwort(e): Enthalpies of reaction ; heats of reaction ; kinetics ; ester hydrolysis ; microcalorimetry
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The conditions under which the Picker flow microcalorimeter can be used to measure enthalpies and rates of reactions were investigated. For this purpose, systematic studies were made of the enthalpies of neutralization of HCl, HBr, HNO 3 , acetic, proprionic, and butyric acids with NaOH, enthalpies of hydrolysis of methyl and ethyl acetate with NaOH, and the reaction rates of the ester hydrolysis with NaOH. The general procedure and various sources of error are discussed and it is concluded that enthalpies of slow reactions can be measured to about 1% when the calorimeter is operated in the quasi-isothermal mode and the reaction rates to about 3% when operated in the quasi-adiabatic mode.
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  • 19
    Digitale Medien
    Digitale Medien
    Springer
    Cellulose 4 (1997), S. 1-5 
    ISSN: 1572-882X
    Schlagwort(e): paper ; degradation ; ageing ; kinetics ; modelling
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Materialart: Digitale Medien
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  • 20
    Digitale Medien
    Digitale Medien
    Springer
    Cellulose 3 (1996), S. 243-267 
    ISSN: 1572-882X
    Schlagwort(e): aging tests ; cellulose degradation ; durability ; kinetics ; paper properties
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract The validity of accelerated aging tests to predict and rank papers on their permanence has been under question, preventing the development of performance-based standards for permanent paper. We conducted a general kinetic analysis to investigate the aging process of paper. A general kinetic model is proposed to describe the depolymerization of cellulose. Experimentally it was shown that in the case of aging, cellulose degradation follows classic first-order kinetics as a special case of our general kinetic model. The Arrhenius equation was critically re-examined for the case of a multiple reaction system. It was shown analytically that the Arrhenius equation is still applicable when certain conditions are met. This was convincingly supported by experimental results. We also analysed the dependence of the degradation rate on the moisture content and hydrogen ion concentration. By conducting systematic experiments on these two factors, a general and quantitative relationship was established to explain the contribution of each factor and their interactions. Finally, based on this kinetic analysis, the effects of storage conditions on the life expectancy of paper were estimated.
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  • 21
    Digitale Medien
    Digitale Medien
    Springer
    Journal of inorganic and organometallic polymers and materials 8 (1998), S. 111-117 
    ISSN: 1572-8870
    Schlagwort(e): Organosiloxane ; kinetics ; poly(phenylmethylsiloxane) ; catalyst ; anionic ; ring-opening
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract It is well known that the rate of polymerization for an anionic mechanism is dependent on the ability of the bulk material or solvent system to disassociate the ion pair at the propagating chain end. In the anionic ring-opening polymerization of cyclic organosiloxanes in particular, the larger and softer the counter ion, the more rapidly the reaction proceeds. A recently developed phosphazene initiator system provides a large, soft counter ion relative to other traditional initiators used for the polymerization of poly(dimethylsiloxane) (PDMS). This novel initiator system was used in this investigation for the ring-opening polymerization of tetraphenyltetramethylcyclotetrasiloxane (P4) and the reaction kinetics under bulk and solution conditions were investigated. The new initiator system showed a dramatic increase in the rate of polymerization over the conventional potassium hydroxide-catalyzed system. Furthermore, this initiator was sufficiently reactive to be useful for the ring-opening polymerization of P4 at 293 K.
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  • 22
    ISSN: 1572-8900
    Schlagwort(e): Cellulose ; alkaline degradation ; peeling off ; degree of polymerization ; kinetics ; (gluco)isosaccharinic acid
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Energietechnik , Maschinenbau
    Notizen: Abstract The degradation of cellulosic materials, differing mainly in the degree of polymerization and the number of reducing end groups, was studied under the alkaline conditions similar to those existing in a cementitious repository for low- and intermediate-level radioactive waste (pH 13.3, T = 25°C). The kinetics of alkaline degradation (peeling-off reaction) were studied and the data analyzed by the model of Haas et al. [13]. The observed kinetic parameters for the propagation reaction and overall stopping reaction were compared with literature data. Although measured under different experimental conditions, literature data and data from this study show a consistent picture. Differences in the extent of degradation observed for the different cellulosic materials could be satisfactorily explained by differences in reducing end group content and, consequently, by differences in the degrees of polymerization. Besides the number of reducing end groups, the degree of amorphousness also plays an important role. The main degradation products formed under the experimental conditions used are α- and β-(gluco)isosaccharinic acid. This is in agreement with many other studies on alkaline degradation of cellulose. The two isomers are formed in roughly equal amounts.
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  • 23
    Digitale Medien
    Digitale Medien
    Springer
    Topics in catalysis 5 (1998), S. 133-147 
    ISSN: 1572-9028
    Schlagwort(e): NMR ; catalysis ; high pressure ; dynamic equilibria ; magnetization transfer ; sapphire tube ; gas phase ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract High resolution NMR techniques are applicable to a variety of aspects of catalysis. Methods for studying homogeneously-catalyzed systems under high gas pressure are described along with approaches for obtaining mechanistic and dynamic information. Many of the same techniques may be applied to heterogeneous catalysis by following the reaction chemistry by gas phase NMR.
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  • 24
    ISSN: 1572-9028
    Schlagwort(e): nonlinear temperature behavior ; Eyring plot ; modified Eyring plot ; selectivity ; selection process ; enantioselectivity ; selection level ; isoinversion principle ; isoinversion temperature ; inversion temperature ; kinetics ; catalysis ; asymmetric hydrogenation ; dihydroxylation ; cocyclization
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The influence of the temperature on selectivity is described under special consideration of nonlinearities in the corresponding modified Eyring plots. Reasons for the experimentally well-known behavior are discussed. Furthermore, the conditions for nonlinear temperature behavior are quantified and a concept is described which allows the determination of the temperature dependence of a single reaction pathway in a selection process.
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  • 25
    ISSN: 1572-8757
    Schlagwort(e): micropore size distribution ; activated carbon ; adsorption ; desorption ; equilibrium ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Physik , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract This paper deals with the prediction of adsorption equilibrium and kinetics of hydrocarbons onto activated carbon samples having different micropore size distribution (MPSD). The microporous structure of activated carbon is characterised by the distribution of slit-shaped micropores, which is assumed to be the sole source of surface heterogeneity. The interaction between adsorbate molecule and pore walls is described by the Lennard-Jones potential theory. Different adsorbates have access to different pore size range of activated carbon due to the size exclusion, a phenomenon could have a significant influence on both multicomponent equilibria and kinetics. Activated carbons with three different MPSDs are studied with ethane and propane as the two model adsorbates. The Heterogeneous Macropore Surface Diffusion model (HMSD) is employed to simulate adsorption kinetics. The simulation results show that the MPSD is an important factor affecting both the multicomponent equilibria and kinetics.
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  • 26
    Digitale Medien
    Digitale Medien
    Springer
    Catalysis letters 60 (1999), S. 51-57 
    ISSN: 1572-879X
    Schlagwort(e): furfural hydrogenation ; Cu/carbon catalysts ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Furfural hydrogenation over copper dispersed on three forms of carbon – activated carbon, diamond and graphitized fibers – were studied. Only hydrogenation of the C=O bond to form either furfuryl alcohol or 2‐methyl furan occurred at temperatures from 473 to 573 K. Reduction at 573 K gave the most active catalysts, all three catalysts had activation energies of 16 kcal/mol, and turnover frequencies were 0.018–0.032 s-1 based on the number of Cu0 + Cu+ sites, which were counted by N2O adsorption at 363 K and CO adsorption at 300 K, respectively. The Cu/activated carbon catalyst showed no deactivation during 10 h on stream, in contrast to the other two catalysts. A simple Langmuir–Hinshelwood model invoking two types of sites was able to fit all kinetic data quite satisfactorily, thus it was consistent with the presence of both Cu0 and Cu+ sites.
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  • 27
    Digitale Medien
    Digitale Medien
    Springer
    Catalysis letters 60 (1999), S. 167-171 
    ISSN: 1572-879X
    Schlagwort(e): ammonia decomposition ; iron catalyst ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The decomposition of ammonia is a reaction associated with the process of the nitriding of metals. The kinetics of the ammonia decomposition on iron catalysts has been studied using a differential reactor with internal mixing. The balance between the inlet and outlet ammonia quantity has been used to determine the degree of conversion. The rate of ammonia decomposition could be described by the following expression: r = k0 exp (Ea/RT)pNH3. The activation energy of the ammonia decomposition process has been found for samples with potassium as E a= 96 kJ/mol, for samples without potassium as E a= 87 kJ/mol.
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  • 28
    ISSN: 1572-8757
    Schlagwort(e): kinetics ; isotope-exchange ; nitrogen ; adsorption ; methane ; zeolite ; equilibria
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Physik , Werkstoffwissenschaften, Fertigungsverfahren, Fertigung
    Notizen: Abstract The Isotope Exchange Technique (IET) was used to simultaneously measure pure and binary gas adsorption equilibria and kinetics (self-diffusivities) of CH4 and N2 on pelletized 4A zeolite. The experiment was carried out isothermally without disturbing the adsorbed phase. CH4 was selectively adsorbed over N2 by the zeolite because of its higher polarizability. The multi-site Langmuir model described the pure gas and binary adsorption equilibria fairly well at three different temperatures. The selectivity of adsorption of CH4 over N2 increased with increasing pressure at constant gas phase composition and temperature. This curious behavior was caused by the differences in the sizes of the adsorbates. The diffusion of CH4 and N2 into the zeolite was an activated process and the Fickian diffusion model described the uptake of both pure gases and their mixtures. The self-diffusivity of N2 was an order of magnitude larger than that for CH4. The pure gas self-diffusivities for both components were constants over a large range of surface coverages (0 〈 θ 〈 0.5). The self-diffusivities of CH4 and N2 from their binary mixtures were not affected by the presence of each other, compared to their pure gas self-diffusivities at identical surface coverages.
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  • 29
    Digitale Medien
    Digitale Medien
    Springer
    BioMetals 10 (1997), S. 23-26 
    ISSN: 1572-8773
    Schlagwort(e): aromatic donor molecules ; horseradish peroxidase ; kinetics ; lactoperoxidase
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Chemie und Pharmazie
    Notizen: Abstract Based on kinetic evidence, it has been shown for the first time that the mode of binding of aromatic donor molecules is similar in horseradish peroxidase and lactoperoxidase; also that the nature of the heme plays an important role in the reaction with hydrogen peroxide, and has no effect on the reaction of the intermediate compound II with aromatic substrates.
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  • 30
    Digitale Medien
    Digitale Medien
    Springer
    Catalysis letters 31 (1995), S. 431-438 
    ISSN: 1572-879X
    Schlagwort(e): partial hydrogenation of benzene ; production of cyclohexene ; kinetics ; reaction mechanism ; ruthenium catalyst
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A method has been developed for direct measurement of reaction rates in a continuously operated slurry (CST-) reactor. In contrast to the usual procedure in a two-liquid-phase system the reactor contains only one liquid phase, an aqueous zinc chloride solution in which a ruthenium lanthanoxide catalyst is suspended. The selectivity of benzene hydrogenation with respect to cyclohexene is higher when the new one-liquid-phase procedure is applied. With decreasing degree of benzene conversion the selectivity with respect to cyclohexene approaches 100%. The conclusion is that cyclohexane is formed only by consecutive hydrogenation of cyclohexene.
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  • 31
    Digitale Medien
    Digitale Medien
    Springer
    Catalysis letters 39 (1996), S. 67-71 
    ISSN: 1572-879X
    Schlagwort(e): non-uniform surface ; kinetics ; ethanol ; oxidation ; molybdenum oxide
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Temkin's theory of rates of catalytic reactions on non-uniform surfaces is extended to the MoO3-catalyzed oxidation of ethanol to acetaldehyde. Two types of sites are assumed to be present, an oxygen atom site that can be modeled with uniform properties and a metal atom site characterized by non-uniform properties both for ethanol chemisorption to an ethoxide intermediate and the conversion of this intermediate to acetaldehyde. The rate-limiting step is the cleavage of a C-H bond in the absorbed ethoxide intermediate. Non-uniform surface kinetics leads to a kinetic rate expression of the form $$v = kP_{C_2 H_5 OH}^{1 - m} P_{O_2 }^{(1 - m)/4} P_{H_2 O}^{ - (1 - m)/2} $$ . Such a rate expression, withm=0.14, is shown to provide a good fit to kinetic data for the selective oxidation of ethanol on a silica supported molybdenum oxide catalyst.
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  • 32
    Digitale Medien
    Digitale Medien
    Springer
    Catalysis letters 36 (1996), S. 31-36 
    ISSN: 1572-879X
    Schlagwort(e): ethanol ; kinetics ; oxidation ; oxydehydrogenation ; platinum ; structure sensitivity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The effect of the platinum particle size was investigated for the catalytic oxidative dehydrogenation of aqueous ethanol to ethanal at a temperature of 303 K, an ethanol concentration of 260 mol m−3, a partial oxygen pressure 60 kPa, a pH of 9, and an ethanal and ethanoate concentration of 20 mol m−3. A particle size effect on the turnover frequency was observed but only for particle sizes smaller than 2 nm. Hence, the reaction shows a limited structure sensitivity.
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  • 33
    Digitale Medien
    Digitale Medien
    Springer
    Catalysis letters 55 (1998), S. 73-77 
    ISSN: 1572-879X
    Schlagwort(e): enantioselectivity ; hydrogenation of ethyl pyruvate ; Pt/alumina catalyst ; solvent effects ; kinetics ; solvent polarity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The influence of solvent on the kinetics of enantioselective hydrogenation of ethyl pyruvate by Pt/Al2O3/dihydrocinchonidine is reported. In a non‐polar solvent, toluene, the reaction is approximately zero order in substrate at constant hydrogen pressure, while under the same conditions and at the same substrate concentration, in the polar solvents ethanol and propylene carbonate the reaction shows a first‐order substrate concentration dependence. Fits to a Michaelis–Menten rate expression show that these differences are the expression of the relative magnitudes of the adsorption term in the rate expression, which in turn reflects the influence of the solvent on the adsorption–desorption processes which take place at the catalyst surface.
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  • 34
    Digitale Medien
    Digitale Medien
    Springer
    Catalysis letters 59 (1999), S. 143-149 
    ISSN: 1572-879X
    Schlagwort(e): hydrogen ; desorption ; copper ; activation energy ; kinetics ; order of desorption
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The kinetics of desorption of hydrogen from the copper component of an alumina-supported polycrystalline copper catalyst has been studied in detail by temperature-programmed desorption (TPD). Line-shape analysis of the hydrogen TPD spectra shows: (i) that the desorption is second order, (ii) that the desorption activation energy is in the range 64–68 kJ mol−1 in the coverage range 7–44% of a monolayer, and (iii) that the desorption pre-exponential term has a value ∼10−5 cm2 s−1 atom−1 consistent with the desorption being second order, involving mobile adsorbates and a mobile desorption transition state.
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  • 35
    Digitale Medien
    Digitale Medien
    Springer
    Microchimica acta 124 (1996), S. 13-25 
    ISSN: 1436-5073
    Schlagwort(e): kinetics ; rates ; integrating ratemeter ; optimization ; first-order
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The integrating ratemeter is used in concert with the two-rate parameter to form the integrating ratemeter two-rate parameter. Propagation of error theory is applied to the integrating ratemeter two-rate parameter to yield expressions for the precision of rates calculated from the integrating ratemeter two-rate parameter in terms of the precision of the rates measured with the integrating ratemeter. Simulations and experimental results show that in cases where the standard deviation of the rate is relatively constant, the optimum time to make a rate measurement using the integrating ratemeter is also the optimum time to measure either of the rates in the two-rate parameter. If either of the two rates comprising the two-rate parameter is measured at the optimum time, then the precision and accuracy of concentrations measured with this technique are optimized.
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  • 36
    Digitale Medien
    Digitale Medien
    Springer
    Nutrient cycling in agroecosystems 51 (1998), S. 209-215 
    ISSN: 1573-0867
    Schlagwort(e): Desorption ; kinetics ; microbial transformation ; phosphate ; soils
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft
    Notizen: Abstract The improvement of P management in agriculture and environment requires a good understanding of residual effect of applied P in soils. The specific adsorption of P on variable charge minerals has been considered as the major mechanism that leads to a very low utilization of P fertilizer by crops within a growing season in Chinese red soils. Soil incubation and isotope tracing analysis were carried out to examine the transformation kinetics and potential availability of added specifically sorbed 32P in two pH contrasting light textured soils. The 32P recovered by 0.5 M NaHCO3 extraction and microbial biomass-P measurement from the added specifically sorbed 32P in the soils was well described by a first-order reaction and a Langmuir-type kinetic model, with correlation coefficients (R) being, on average, 0.938 and 0.959, respectively. The half-life (t1/2, from the first-order model) of the four tested mineral-P complexes ranged from 29 to 47 d in the acid sandy soil and 33 to 105 d in the neutral silty soil. Goethite-P was the most stable among the four tested mineral-P complexes. The potential availability of the mineral complex P (q m , in percent of total 32P added) obtained from the Langmuir equation ranged from 43.7 to 90.9% for the four mineral-P complexes, and decreased in the order: Al oxide-P (90.9%) 〉 montmorillonite-P (86.2%) 〉 kaolinite-P (77.5%) 〉 goethite-P (60.2%) in the acid sandy soil, whereas the order was Al oxide-P (89.3%) 〉 kaolinite-P (86.2%) 〉 montmorillonite-P (82.6%) 〉 goethite-P (43.7%) in the neutral silty soil. Based on the release rate and potential availability, kaolinite-P and Al oxide-P could be important sources for residual effect of applied P in variable-charge soils. The goethite-P has the lowest release rate and potential availability among the mineral-P complexes, implying that iron oxides may be the most important variable-charge mineral responsible for P fixation in the Chinese red soils.
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  • 37
    Digitale Medien
    Digitale Medien
    Springer
    Journal of statistical physics 95 (1999), S. 23-43 
    ISSN: 1572-9613
    Schlagwort(e): model alloy ; Monte Carlo ; elastic interactions ; phase separation ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Physik
    Notizen: Abstract We study via Monte Carlo simulations the influence of elastic interactions on the ordering and decomposition of a two-dimensional model binary alloy with antiferromagnetic nearest and ferromagnetic next nearest neighbor type interactions following a quench into the coexistence region. The elastic interaction leads to the development of a platelet morphology for the segregated ordered and disordered regions. A length scale characterizing the coarsening process follows a law of the type R=a+bt 1/3 with the growth b decreasing with the amount of ordered phase; this appears to be due to the presence of anti-phase boundaries between neighboring domains ordered on different sublattices which are difficult to eliminate. The application of uniaxial external stress results in “rafting” of the domains. Many of the simulation results are in agreement with experimentally observed effects in nickel-base superalloys.
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  • 38
    ISSN: 1572-9729
    Schlagwort(e): bioavailability ; builders ; detergents ; kinetics ; mineralization ; sewage sludge ; soil
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Energietechnik , Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft
    Notizen: Abstract Tetradecenyl succinic acid (TSA) is the major component of a detergent builder (C12-C14 alkenyl succinic acid), which is inherently biodegradable. 14C-TSA was dosed as a component of sewage sludge into a soil with a history of sludge amendment at final added concentrations of 1.5 and 30 mg (kg soil)-1. In addition, it was dosed to the soil in an aqueous solution to a final added concentration of 30 mg (kg soil)-1. Dose and form were found to have a pronouced effect on the mineralization kinetics. When dosed in a realistic form and concentration (i.e. 1.5 mg (kg soil)-1 as a component of sludge), TSA was mineralized at its highest rate and to its greatest extent, and the mineralization half-life was 2.4 days. When dosed at 30 mg (kg soil)-1 as a component of sludge, mineralization began immediately, and the half-life was 23 days. In contrast, when dosed at this concentration in aqueous solution, the onset of mineralization was preceded by a 13 day lag period and the mineralization half-life was 69 days. Primary biodegradation and mineralization rates of TSA were very similar. Approximately, half the radioactivity was evolved as 14CO2, while the remaining radioactivity became non-extractable, having presumably been incorporated into biomass or natural soil organic matter (humics). This study demonstrated that TSA is effectively removed from sludge-amended soils as a result of biodegradation. Furthermore, it showed the effect that dose form and concentration have on the biodegradation kinetics and the importance of dosing a chemical not only at a relevant concentration but also in the environmental form in which it enters the soil environment.
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  • 39
    ISSN: 1572-9729
    Schlagwort(e): bacteria ; degradation ; denitrification ; kinetics ; stoichiometry ; toluene
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Energietechnik , Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft
    Notizen: Abstract Batch experiments were carried out to investigate the stoichiometry and kinetics of microbial degradation of toluene under denitrifying conditions. The inoculum originated from a mixture of sludges from sewage treatment plants with alternating nitrification and denitrification. The culture was able to degrade toluene under anaerobic conditions in the presence of nitrate, nitrite, nitric oxide, or nitrous oxide. No degradation occurred in the absence of Noxides. The culture was also able to use oxygen, but ferric iron could not be used as an electron acceptor. In experiments with14C-labeled toluene, 34%±8% of the carbon was incorporated into the biomass, while 53%±10% was recovered as14CO2, and 6%±2% remained in the medium as nonvolatile water soluble products. The average consumption of nitrate in experiments, where all the reduced nitrate was recovered as nitrite, was 1.3±0.2 mg of nitrate-N per mg of toluene. This nitrate reduction accounted for 70% of the electrons donated during the oxidation of toluene. When nitrate was reduced to nitrogen gas, the consumption was 0.7±0.2 mg per mg of toluene, accounting for 97% of the donated electrons. Since the ammonia concentration decreased during degradation, dissimilatory reduction of nitrate to ammonia was not the reductive process. The degradation of toluene was modelled by classical Monod kinetics. The maximum specific rate of degradation, k, was estimated to be 0.71 mg toluene per mg of protein per hour, and the Monod saturation constant, K s , to be 0.2 mg toluene/l. The maximum specific growth rate, μ max , was estimated to be 0.1 per hour, and the yield coefficient, Y, was 0.14 mg protein per mg toluene.
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  • 40
    Digitale Medien
    Digitale Medien
    Springer
    Biodegradation 7 (1996), S. 73-81 
    ISSN: 1572-9729
    Schlagwort(e): diesel oil ; biodegradation ; CSTR ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie , Energietechnik , Land- und Forstwirtschaft, Gartenbau, Fischereiwirtschaft, Hauswirtschaft
    Notizen: Abstract In batch culture diesel oil was degraded rapidly, with a maximum growth rate (for a consortium of microorganisms) of 0.55 h-1. The corresponding yield Y SX was 0.1 Cmol/Cmol. In a continuous stirred tank reactor the maximum dilution rate was about 0.25 h-1, with a yield of 0.3 Cmol/Cmol. With a residence time of 1 day 82% of the influent oil was degraded. In the batch reactor, of the mixture of linear and branched alkanes the linear alkanes were degraded fastest and with the highest yield. Only after most of the linear alkanes had disappeared were the branched alkanes consumed. In a CSTR a large part of the branched alkanes was not degraded.
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  • 41
    Digitale Medien
    Digitale Medien
    Springer
    Pure and applied geophysics 147 (1996), S. 367-375 
    ISSN: 1420-9136
    Schlagwort(e): Induced seismicity ; kinetics ; rock fracture ; rockburst ; earthquake
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Geologie und Paläontologie , Physik
    Notizen: Abstract Powerful seismic events, such as earthquakes and rockbursts, are caused by the accumulation of energy in rocks and loss of rock mass stability. Usually methods of their forecasting are based on the registration of anomalous behavior of geophysical fields. However an efficiency of this approach is low. The present paper proposes a kinetic approach to the description of rock fracture process, which can be used for the forecasting of seismic events and an investigation of structure and energy distributions in rock. 3-D and 1-D kinetic equations describing a process of cluster formation in rock were obtained. The equations are invariant to deformation conditions and to the scale level of events. They showed a good agreement with the results of field observations and laboratory experiments. It was also shown that these equations well describe the processes of earthquake, rockburst and rock sample failure preparation. Catalogues of rockbursts in mines were analyzed with the use of the kinetic equations to find out evidence of induced seismic events. The proposed approach makes it possible to reveal trends in rock behavior and thus predict the rock failure at different scale levels.
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  • 42
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 52 (1997), S. 505-506 
    ISSN: 1432-1041
    Schlagwort(e): Key words Ibuprofen; effervescent tablets ; kinetics ; bioavailability
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Materialart: Digitale Medien
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  • 43
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 21 (1981), S. 215-220 
    ISSN: 1432-1041
    Schlagwort(e): phenytoin ; cimetidine ; antipyrine test ; drug interaction ; drug metabolism ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary In a prospective study in nine patients the effects of phenytoin and of cimetidine (1000mg/day) + phenytoin on the antipyrine test and serum phenytoin concentrations were studied. Serum phenytoin increased from the steady state level of 5.7±1.3 mg/l to 9.1±1.4mg/l after three weeks on cimetidine (p〈0.01), and fell to 5.8±1.2 mg/l within two weeks after withdrawal of cimetidine. The protein binding of phenytoin was not changed by cimetidine. After use of phenytoin for 2–4 months, antipyrine clearance increased from 0.67±0.06ml/min/kg to 1.61±0.22 ml/ min/kg, and antipyrine half-live fell from 10.9±1.3h to 4.5±0.6h as compared to the values before phenytoin treatment (p〈0.01). After three weeks combined use of cimetidine and phenytoin, antipyrine clearance was decreased to 1.01±0.07 ml/min/kg and antipyrine half-life was prolonged to 6.1±0.5h, (p〈0.01) compared to the values on phenytoin alone. The distribution volume of antipyrine was not affected by phenytoin nor by cimetidine + phenytoin. The half-life of cimetidine was 2.8±0.3h in the patients on longterm phenytoin treatment. There was a significant positive correlation (p〈0.001) between the increase in serum phenytoin concentration and the prolongation of antipyrine half-life caused by cimetidine. Thus, cimetidine increases serum phenytoin concentration, very probably by inhibiting its metabolism. Care should be taken in the concomitant use of cimetidine and phenytoin, and the dose of phenytoin should be modified according to the clinical symptoms and serum phenytoin concentrations.
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  • 44
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 22 (1982), S. 225-228 
    ISSN: 1432-1041
    Schlagwort(e): pinazepam ; N-desmethyldiazepam ; kinetics ; metabolism ; human
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary The plasma profile of a single oral dose of pinazepam 10 mg was studied in 6 healthy male volunteers, aged 26 to 31 years. The concentrations of the parent compound and of its metabolite in plasma were measured by gas-chromatography. The peak plasma levels of pinazepam was 36.8±5.1 ng/ml and of N-desmethyldiazepam 150±13.3 ng/ml. The plasma concentration of the metabolite become higher than that of the parent compound shortly after administration, suggesting that pinazepam acts as a prodrug.
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  • 45
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 22 (1982), S. 545-551 
    ISSN: 1432-1041
    Schlagwort(e): oxcarbazepine ; kinetics ; disposition ; metabolites ; renal excretion ; volunteers
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary Oxcarbazepine (oxcarb) 600 and 900 mg (2360 and 3540 µmol) was taken by 3 volunteers (2 ♀, 1 ♂; 45–67 kg; age 22–34 years) after an overnight fast. Blood, saliva and urine were collected for the next 72 h for assay of oxcarb, 10,11-dihydro-10-hydroxy-carbamazepine (OHcarb), and 10,11-dihydrotrans-10,11-dihydroxy-carbamazepine (diol). Oxcarb reached a maximum level of about 1 µg/ml (3.93 µmol/l) within 1 h and dropped below the detection limit (0.1 µg/ml=0.39 µmol/l) within 3 h. The active metabolite OHcarb appeared in the blood before oxcarb and reached the higher maximum level of 7.4 µg/ml (29 µmol/l) after 7 h. Thereafter serum levels decreased with a t1/2 of about 25 h, and after 40 h with a t1/2 of 9 h, the latter agreeing with the renal excretory t1/2 calculated from the urine data (10 h). The ratio of OHcarb concentration in saliva to that in plasma varied considerably (0.3–1.7; median 1; r〉0.9), whereas that of blood to plasma was 1.25 with only small variation (r〉0.98); OHcarb concentrations in erythrocytes were 50% higher than in plasma. Diol was detected in blood (maximum level 0.5 µg/ml=1.84 µmol/l) in 2 volunteers. 45% of the dose could be recovered in urine (Oxcarb 5%, OH-carb 36%, Diol 4%). Whereas Oxcarb was completely conjugated, only 25% of OHcarb was conjugated and diol was unconjugated.
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  • 46
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 24 (1983), S. 217-220 
    ISSN: 1432-1041
    Schlagwort(e): metoprolol ; pregnancy ; hypertension ; kinetics ; pre-eclampsia
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary The disposition of oral metoprolol was studied in 5 women during the last trimester of pregnancy and 3 to 5 months after delivery. After a single oral dose of 100 mg the individual peak plasma concentration in the pregnant state was only 20–40% of that after pregnancy. The plasma half-lives of metoprolol were about the same during (average 1.3 h) and after pregnancy (average 1.7 h). By contrast, the area under the plasma concentration versus time curve was much smallerduring (mean 262 nmol/l×h) thanafter (mean 1298 nmol/l×h) pregnancy, resulting in an average apparent oral clearance (Clo) of metoprolol that was 4.4times higher during (362 ml×kg−1 body-weight×min−1) than after pregnancy. The increased Clo in pregnancy is assumed to be due to enhanced hepatic metabolism of the drug. The possible clinical consequence of the difference in the disposition of metoprolol is discussed.
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  • 47
    ISSN: 1432-1041
    Schlagwort(e): prizidilol ; antihypertensive effect ; acute and long-term blood pressure control ; plasma renin activity ; acetylator phenotype ; antinuclear antibodies ; side effects ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary After an initial placebo period of four weeks 24 patients with primary hypertension were treated with prizidilol, a hydrazinopyridazine derivative with combined vasodilator and non-selective beta-adrenoceptor blocking actions, for a dose titration period of 14 weeks. Prizidilol 200 to 800 mg was given once daily to achieve a target supine diastolic blood pressure (BP)〈90 mmHg. Supine and standing BP recorded 24–27 h after drug intake decreased from 172±17/106±6 mmHg (mean±SD) and 167±18/111±8 mmHg, respectively, after placebo to 159±16/99±8 and 154±18/101±9 mmHg after active treatment for six weeks (mean dose 447 mg), and to 154±16/97±7 and 148±14/97±7 mmHg after treatment for 14 weeks (mean dose 687 mg/day). A slight reduction in HR was seen after treatment for six weeks and in plasma renin activity and urinary methoxycatecholamine excretion after treatment for 14 weeks. A sustained decrease in BP was observed for 10 h after prizidilol 800 mg (n=9), with a maximum antihypertensive effect (mean reduction in supine BP 33/18 mmHg) 2.5 h after dosing, which coincided with the mean peak plasma concentration. The plasma elimination half-life of the drug was 3.9 h (range 2.0–8.9 h). Changing to a twice daily regimen in 17 patients (mean daily dose 748 mg at six months) did not produce any further reduction in the BP (recorded 12–15 h after dosing) as compared to the once daily regimen at 14 weeks. During treatment for up to 24 months, 16 patients did not achieve satisfactory BP control. Eight of them were withdrawn and eight received additional treatment with bendroflumethiazide (2.5–5 mg/day). In 7 of the latter satisfactory BP control was achieved. Side effects were few. Dizziness and tiredness occurred in four patients 2–5 h after prizidilol 600–800 mg once daily. These symptoms partly subsided when the subjects changed to a twice daily regimen. No ocular side-effects were found. Before treatment 13 out of 24 patients had a low titre of IgM antinuclear antibodies (ANA) and one patient also a low titre of IgG ANA. During treatment the frequency of patients with positive ANA-titres became higher, and after treatment for 12 months (n=17) 15 patients had positive IgM and seven patients positive IgG ANA-titres. However, the titres were low and no patient showed a clinical lupus erythematosus syndrome. There was no relation between acetylator phenotype of the patient and acute or longterm effecton BP, pharmacokinetics of the drug or the development of a raised ANA-titre.
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  • 48
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 24 (1983), S. 273-276 
    ISSN: 1432-1041
    Schlagwort(e): undernourished ; chlorquine ; kinetics ; plasma levels ; red cell uptake
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary The plasma and whole blood kinetics of chloroquine was studied in 7 normal and 8 undernourished subjects following a single oral dose of 600 mg. The terminal half-lives were similar in both groups. The AUC was also similar in the 2 groups, even though a higher dose per kg body weight was administered to the undernourished. This was probably because of faster clearance in this group. Chloroquine uptake by erythrocytes, its main site of action in malaria, was also comparable in the two groups. The plasma concentration of chloroquine over a period of time was found to be similar in 4 normal and 4 undernourished subjects following administration of 1.5 g of the drug in divided doses. The undernourished appear, therefore, to handle chloroquine in such a way that they do not suffer a greater risk of toxicity than normals.
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  • 49
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 24 (1983), S. 525-527 
    ISSN: 1432-1041
    Schlagwort(e): theophylline ; airway obstruction ; biotransformation ; kinetics ; oral dosage
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary Oral theophylline was given to 6 adults with airways obstruction. The initial dose was 125 mg daily and this was increased by 125 mg each week. The final total daily dose reached was determined by side effects and ranged from 500 mg to 1125 mg. At the end of each week and before the next dosage increment steady state, trough plasma theophylline concentrations were measured. For each individual and for the group as a whole there was a highly significant linear correlation between theophylline dose and trough plasma concentration. This indicates that for oral theophylline, in adults, dose-dependent kinetics do not play a significant role and dose may be adjusted without fear of a disproportionate rise in plasma concentration.
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  • 50
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 27 (1984), S. 491-494 
    ISSN: 1432-1041
    Schlagwort(e): amiodarone ; kinetics ; volunteers
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary We studied three healthy volunteers after a single i.v. bolus of amiodarone, during 1 month of chronic oral dosing and after the discontinuation of the drug. Blood concentrations of amiodarone declined rapidly in a bi-exponential fashion after i.v. bolus. The terminal half-life ranged from 10 to 17 h; after discontinuation of chronic treatment the terminal half-lives were 8–21 days. The i.v. data, the trough levels during multiple dosing and the washout phase could be simultaneously fitted using a tri-exponential equation. The subjects were carefully monitored for cardiac and thyroid function. One subject had to stop taking amiodarone because of profound bradycardia. A reduction of serum TT3 and FT3 concentrations and an increase of serum rT3 and FT4 was found.
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  • 51
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 17 (1980), S. 285-293 
    ISSN: 1432-1041
    Schlagwort(e): tolbutamide ; chlorpropamide ; kinetics ; food ; age ; blood glucose ; plasma insulin
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary The influence of food intake (standardized breakfast) on the oral single-dose kinetics and effects of tolbutamide (0.5 g) and chlorpropamide (250 mg) was investigated in young, healthy volunteers. The single-dose kinetics of the two drugs was also studied in elderly healthy subjects. There was great interindividual variation in the elimination rate of both drugs, but food intake influenced neither their AUCs nor their rates of absorption and elimination. The peak concentration of chlorpropamide, but not that of tolbutamide, was reduced by food intake. The peak concentrations of serum tolbutamide were approximately doubled by an increase in dose from 0.5 to 1.0 g, and from 1.0 to 2.0 g. At no time did tolbutamide 0.5 g affect the plasma insulin level, neither in the fasting nor in the non-fasting state. However, this dose did reduce the blood glucose level during fasting and the increase in blood glucose in response to the meal. The latter effect was recorded within 30 min, when the serum level of tolbutamide still was close to zero. Plasma insulin concentrations did increase within 30 min after a higher dose of tolbutamide (1.0 g), when the serum concentration of tolbutamide was about 50 µmol/l. Between 2.5 and 8 h after administration of chlorpropamide 250 mg, serum drug concentrations were lower than those following tolbutamide 0.5 g. The blood glucose response was smaller and occurred later, being significant at 2 h, when the serum concentration of the drug was about 70 µmol/l. There was no significant change in plasma insulin. There was no significant pharmacokinetic difference between young and elderly subjects, except that the peak concentration of tolbutamide was higher in the latter. It appears that both for tolbutamide and chlorpropamide there is great interindividual variation in drug disposition, but food intake does not influence the bioavailability of either drug. The effect of any particular drug concentration seems dependent upon the blood glucose level and hence upon the elapsed time since the last meal. Both drugs can reduce blood glucose without an alteration in the peripheral blood concentration of insulin. This may reflect an extrapancreatic effect of the drugs, but it could also be an expression of increased insulin secretion, which is not detected because of enhanced hepatic degradation of the hormone released into the portal circulation. The observations made in young individuals are also probably relevant for elderly subjects.
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  • 52
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 21 (1982), S. 403-408 
    ISSN: 1432-1041
    Schlagwort(e): glibenclamide ; diabetes ; insulin ; kinetics ; blood glucose ; relationship to meals ; absorption
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary In an attempt to assess whether intake of glibenclamide before meals would improve its therapeutic capacity, the present investigation compared the effect of glibenclamide 2.5mg t.i.d. given before and together with meals. In addition, these effects were compared with that of glibenclamide given as a single morning dose of 7.5mg. The subjects studied were six Type 2 diabetics not previously exposed to sulphonylurea drugs. Irrespective of dosage and mode of administration, addition of glibenclamide to a standardized breakfast, lunch and dinner enhanced plasma IRI concentrations and reduced blood glucose concentrations as compared to administration of meals without the drug. The different modes of glibenclamide administration did not differ significantly with respect to IRI responses. However, the blood glucose reduction after breakfast was significantly greater when glibenclaimde 2.5mg had been given before the meal than when 2.5 or 7.5mg were given with the meal; a similar, but non-significant tendency was observed after lunch; no consistent difference was seen after dinner. Food intake did not affect glibenclamide kinetics. It appears that administration of glibenclamide 2.5mg before breakfast improved glucose utilization following the breakfast load, due to earlier attainment of an effective concentration of glibenclamide.
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  • 53
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 22 (1982), S. 309-314 
    ISSN: 1432-1041
    Schlagwort(e): acetylsalicylic acid ; salicylic acid ; dipyridamol ; bioavailability ; kinetics ; rapid- and slow-release formulations
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary Acetylsalicylic acid (ASA) is a strong, irreversible inhibitor of platelet aggregation, but loses this activity following first-pass deacetylation to salicylic acid (SA). In order to compare the bioavailability of unchanged ASA from rapid- and slow-release formulations, the single-dose concentration profiles of ASA and SA were studied in healthy volunteers following intake of two different rapid-release (conventional and effervescent tablets) and three different slow-release (microencapsulated ASA in tablets and in capsules, and enteric-coated tablets) formulations of ASA, and of one slow-release formulation of sodium salicylate. Since anti-platelet therapy with ASA is often combined with dipyridamol, the influence of this drug was also examined. The concentrations of ASA and SA were measured by high-pressure liquid chromatography. While the bioavailability of SA from the 5 ASA formulations was essentially equal and similar to that of the salicylate formulation, the bioavailability and peak concentrations of ASA appeared to be the much greater after rapid-release than after slow-release formulations. Indeed, ASA was only rarely detected in systemic blood following intake of slow-release ASA. Co-administered dipyridamol did not significantly influence the kinetics of ASA or SA. It appears that rapid-release formulations of ASA should be prefered in anti-platelet therapy, either alone or in combination with dipyridamol.
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  • 54
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 24 (1983), S. 41-47 
    ISSN: 1432-1041
    Schlagwort(e): quinidine ; digoxin ; interaction ; kinetics ; absorption ; elimination
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary To evaluate the possible effect of quinidine on digoxin bioavailability, the steady state digoxin kinetics was examined with and without concomitant quinidine therapy, in 7 cardiac patients after simultaneous administration of oral digoxin and intravenous [3H]-digoxin. In the presence of quinidine, the absorption rate constant of digoxin (ka) increased from 2.72±1.04 to 3.53±1.34 h−1 (p〈0.05), whereas lag time and peak time decreased from 0.16±0.10 to 0.05±0.04 h (p〈0.05) and from 0.92±0.27 to 0.69±0.19 h (p〈0.02), respectively. Predose plasma digoxin increased from 0.41±0.25 to 0.70±0.31 ng/ml (p〈0.02), while peak plasma digoxin increased from 0.93±0.34 to 1.63±0.46 ng/ml (p〈0.02). The systemic availability of digoxin increased from 68.48±13.35 to 79.09±14.89% (p〈0.05) in the presence of quinidine. Quinidine had no effect on the biotransformation pattern of digoxin, as assessed by thin layer chromatography. Quinidine increases the rate and extent of digoxin absorption, and this interaction contributes significantly to the elevation in plasma digoxin during both its distribution and elimination phases.
    Materialart: Digitale Medien
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  • 55
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 24 (1983), S. 517-519 
    ISSN: 1432-1041
    Schlagwort(e): lorcainide ; oral antiarrhythmic therapy ; nor-lorcainide ; first-pass metabolism ; kinetics ; alternative dosage ; regimens
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary The feasibility of giving a supplementary starting dose of the antiarrhythmic drug lorcainide, in order to minimalize the impact of the extensive, but saturable first-pass metabolism, was evaluated. Twenty-five adult patients were given 100 mg lorcainide tablets according to one of 3 different dosage schedules: Eight patients took one tablet at 0, 12 and 24h, 8 took 1 tablet at 0, 1, 12 and 24h and 9 took 1 tablet at 0, 2, 12 and 24h. Levels of lorcainide and its metabolite, nor-lorcainide, during treatment were determined by gas-liquid chromatography. The results show that giving a second tablet 1 or 2h after the first may produce faster saturation of the pre-systemic metabolism of lorcainide in the liver.
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  • 56
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 24 (1983), S. 801-806 
    ISSN: 1432-1041
    Schlagwort(e): acebutolol ; hydrochlorothiazide ; kinetics ; drug combination ; interaction ; diacetolol ; healthy subjects ; renal clearance
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary The pharmacokinetics of acebutolol and hydrochlorothiazide (HCT) alone or in combination were studied in 12 healthy subjects in a cross over study. Acebutolol and diacetolol (the main metabolite) in plasma and urine were determined by HPLC and hydrochlorothiazide by GLC. The main pharmacokinetic parameters of acebutolol did not differ significantly: AUC 4492±272 µg l−1 h given alone versus 4118±354 µg l−1 h with HCT, half-life (7,69±0,32 h vs 8,10±0,72 h) and renal clearance (13,1±0,5 lh−1 vs 13,8±0,9 lh−1), respectively. There was no difference in diacetolol pharmacokinetics. HCT values were not significantly different: AUC 784±48 µg l−1 h given alone and 720±42 µg l−1 h with acebutolol, t1/2 (4,79±0,37 h vs 4,73±0,43 h). The renal clearance was slightly higher when HCT was given with acebutolol (26,2±2,6 vs 20,3±2,11 h−1,p〈0,05). This increase, observed during the first four hours, was probably due to competition between the drugs for binding to red blood cells.
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  • 57
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 23 (1982), S. 261-266 
    ISSN: 1432-1041
    Schlagwort(e): mexiletine ; rifampicin ; kinetics ; enzyme induction ; excretion ; antipyrine clearance ; dosage adjustment
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary To study the effects of enzyme induction on its pharmacokinetics, a single oral dose of the new antiarrhythmic agent mexiletine hydrochloride 400 mg was administered to 8 healthy volunteers before and after treatment with rifampicin 300 mg b.i.d. for ten days. The absorption and distribution of mexiletine were not changed after rifampicin, but its elimination half-life fell from 8.5±0.8 h (mean±SE) to 5.0±0.4 h (p〈0.01), and its nonrenal clearance increased from 435±68 ml/min to 711±101 ml/min (p〈0.01). The mean renal clearance of mexiletine did not change, but it showed an exponential correlation with urinary pH. The amount of unchanged mexiletine excreted in urine over two days decreased from 32±7 to 18±3 mg (p〈0.01). The half-life of antipyrine fell from 11.8±0.4 to 5.5±0.3 h and its clearance increased from 40±3 ml to 74±3 ml/min (p〈0.01). There was a significant (p〈0.05) positive linear correlation between both the half-lives and the clearances of antipyrine and mexiletine. The clearances were positively correlated with serum γ-glutamyl transpeptidase. The results suggest that the dosage of mexiletine should be adjusted when enzyme inducing drugs are started or stopped during therapy with it.
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  • 58
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 23 (1982), S. 87-92 
    ISSN: 1432-1041
    Schlagwort(e): phenobarbital ; epilepsy ; kinetics ; bioavailability ; epileptic patients
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary The kinetics of phenobarbital (PB) were evaluated in six normal subjects and six epileptic patients treated with phenytoin or carbamazepine. Each normal subject received three single doses of PB: PB-sodium 130 mg i.v. (IV), PB sodium 130 mg i.m. (IM), and PB acid 100 mg orally (PO), in random order at least one month apart. After IV PB distributive half-lives varied from 0.13 to 0.70 h, disposition half-lives were 75 to 126 h, steady state volume of distribution (Vss) was 0.54±0.03 l/kg, and clearance (CL) was 3.8±0.77 ml/h/kg. Absolute bioavailability of IM PB was 101±13%, of PO PB (corrected for dose) 100±11%. Peak serum PB concentrations were achieved from 2 to 8 h after IM administration, and from 0.5 to 4 h after PO administration. Epileptic patients exhibited similar PB kinetics: disposition half-lives were 77 to 128 h, Vss 0.61±0.05 l/kg, and Cl 3.9±0.76 ml/h/kg. Phenobarbital appears to represent an exception among antiepileptic drugs, in that pharmacokinetic data obtained in normals can reasonably be extrapolated to the epileptic population.
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  • 59
    ISSN: 1432-1041
    Schlagwort(e): metoprolol ; age ; disposition ; elderly subjects ; kinetics ; metabolism ; alpha-OH-metoprolol
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary The absorption and disposition of metoprolol have been evaluated in 10 healthy, non-smoking, elderly individuals (mean age 73.1 years) by simultaneous determination of [3H]-metoprolol and unlabelled metoprolol. The labelled drug was given as an intravenous tracer dose, immediately followed by oral metoprolol 25 mg. The experiment was preceded by administration of metoprolol 25 mg b.i.d. for 3 days. The volume of distribution, elimination half-life and total body clearance were almost the same as previously observed in healthy, young subjects. The mean systemic availability was about 39% in the elderly, which is lower than the mean of 55% observed in a control group of young volunteers who received 50 mg b.i.d. In the elderly, the mean plasma concentration of α-OH-metoprolol was about twice as high as that of the parent drug, whereas the opposite was true of the control group. The results indicate that age-related physiological changes have a negligible effect on the pharmacokinetics of metoprolol.
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  • 60
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 21 (1981), S. 149-153 
    ISSN: 1432-1041
    Schlagwort(e): cinromide ; epilepsy ; kinetics ; metabolites
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary Cinromide is an experimental anticonvulsant currently in phase II testing. A single oral dose (900 mg) of cinromide was administered to 8 epileptic subjects on phenytoin therapy. Plasma samples drawn during the next 36 h were analyzed for cinromide and its amide and acid metabolites. The absorption rate of cinromide varied widely between subjects producing maximum cinromide concentrations between 0.5 and 2.5 h after the dose. The median elimination half lives of cinromide and the amide and acid metabolites were 0.73, 1.65, and 4.85 h respectively. The oral clearance of cinromide (median=135 l/h) suggests that it is subject to first pass metabolism. In all subjects the area under the curve (AUC) of acid metabolite (632 to 1777 µM/l) was greater than the AUC of amide metabolite (77 to 185 µM/l) which was greater than the AUC of cinromide (5 to 89 µM/l). Steady-state concentration ratios of metabolite to parent drug predicted from the AUC data were 3.8 for the amide and 35.8 for the acid metabolite. The amide metabolite is known to have anticonvulsant properties and, until the relative contributions of metabolites and parent drug to the efficacy of cinromide are resolved, the monitoring of metabolites as well as parent drug is imperative.
    Materialart: Digitale Medien
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  • 61
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 21 (1982), S. 379-384 
    ISSN: 1432-1041
    Schlagwort(e): hyperthyroidism ; propranolol ; methimazole ; metoprolol ; atenolol ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary The kinetic profiles of oral methimazole 40mg, propranolol 80mg, metoprolol 100mg and atenolol 100mg were compared in hyperthyroid patients both during the hyper-and euthyroid states. For methimazole, neither the peak concentration (Cmax), the time to reach peak concentration (tmax), the elimination half-life (t1/2) nor the area under the curve (AUC) value was affected by the hyperthyroid state. For propranolol and metoprolol, which undergo extensive presystemic clearance, the AUC values were lower (p〈0.02) when the patients were hyperthyroid than when they had become euthyroid, but the t1/2's were not significantly altered. For atenolol, there were no significant kinetic differences between the hyperthyroid and euthyroid states. The findings are compatible with the assumption that hyperthyroidism does not affect the kinetics of methimazole or atenolol, but that it may enhance presystemic clearance of propranolol and metoprolol.
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  • 62
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 27 (1984), S. 233-236 
    ISSN: 1432-1041
    Schlagwort(e): glibenclamide ; acarbose ; kinetics ; alpha-glucosidase inhibitor ; blood glucose control ; plasma insulin ; Type 2 diabetes
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary A single dose of glibenclamide 5 mg was administered to six Type 2 diabetics, randomly treated for 7 days either with acarbose (3×100 mg daily) or with placebo. The serum concentration of the drug was measured for 10 h. Peak concentrations, times-to-peak concentration, elimination half-lives and the extent of bioavailability of the drug were not significantly modified by acarbose. The combined administration of glibenclamide and acarbose resulted in a modest improvement in the blood glucose profile after breakfast and lunch, together with a significant diminution in plasma insulin. Thus, acarbose appears a useful additional treatment for Type 2 diabetics already receiving sulphonylurea derivatives.
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  • 63
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 26 (1984), S. 521-530 
    ISSN: 1432-1041
    Schlagwort(e): chloroquine ; malaria ; rheumatoid disease ; kinetics ; major metabolite ; optimal dosage ; therapeutic regime ; monodesethylchloroquine ; bidesethylchloroquine
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary The kinetics and disposition of chloroquine (CQ) and its metabolite monodesethylchloroquine (CQM) were investigated in 5 healthy volunteers after incremental (150–300–600 mg CQ base) single oral doses of CQ. The analytical method used (HPLC and fluorescence detection) is the most sensitive known method for CQ and CQM. Plasma and whole blood concentrations of CQ, CQM and a third metabolite, bidesethylchloroquine (CQMM), were determined. The kinetics of CQ was found to be unique. The best fit was obtained by a multicompartmental model. The biological half-life appeared to be between 30–60 days; the volume of distribution (Vd) was ∼ 800l/kg, and the clearance ∼ 11/h/kg when calculated from plasma data. The whole blood concentrations were ∼ 8–10 times higher than in plasma, and consequently the Vd and whole blood clearance were ∼ 10 times lower. The kinetics changed as the dose was increased. An indication of capacity-limited steps in CQ disposition was found, as the rate constants decreased even though the clearance remained the same. The intrinsic half-life of CQM was 1/4 of that of CQ, but was prolonged after the highest dose of CQ. The present knowledge of CQ kinetics could provide a basis for revision of current dosage regimens in malaria suppression and rheumatoid disease to ensure efficacious and safe therapy.
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  • 64
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 27 (1984), S. 367-369 
    ISSN: 1432-1041
    Schlagwort(e): flurbiprofen ; syrup ; suppository ; kinetics ; children ; bioavailability
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary Eight subjects, aged 6–12 years and weighing 18.8–36.7 kg, received single doses of flurbiprofen 50 or 75 mg (corresponding to 1.4–2.7 mg/kg) as syrup and suppository in a Latin square design. Half-life (2.7–3.2 h), elimination constant (0.22–0.26 h−1), area under the plasma level curve (72.4–77.3 µg·h·ml−1) and time to reach the concentration peak (1–0.75 h) were similar after the syrup and suppository. Flurbiprofen showed equivalent bioavailability after oral and rectal administration and the same pharmacokinetic profile was confirmed in children as observed in adults.
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  • 65
    ISSN: 1432-1041
    Schlagwort(e): Key words Diphemanil methylsulphate ; Neonate; antimuscarinic agent ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Materialart: Digitale Medien
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  • 66
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 22 (1982), S. 39-45 
    ISSN: 1432-1041
    Schlagwort(e): furosemide ; neonates ; kinetics ; placental transfer ; intravenous therapy
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary The pharmacokinetics of furosemide was evaluated in 12 newborns who received the drug transplacentally, and in 21 neonates who received it directly for therapeutic reasons. In the first group, the apparent plasma half-lives ranged from 96 to 6.8 h with a significant inverse relationship (p〈0.01) between the gestational age and the elimination rate. In two cases a clear effect on diuresis was also observed. In the neonates receiving the drug i.v. for therapeutic reasons, the elimination kinetics appeared to follow a two-compartment open model, with a significant difference in the therminal plasma half-life between premature (26.8±12.2 h) and full-term newborns (13.4±8.6 h). In this group no relationship was observed between elimination rate and either gestational or conceptional age. In the case of repeated administration, an increase in plasma clearance and reduction in t1/2 β was noticed.
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  • 67
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 22 (1982), S. 435-439 
    ISSN: 1432-1041
    Schlagwort(e): azlocillin ; kinetics ; biliary excretion ; liver dysfunction
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary The pharmacokinetic of azlocillin was followed in five elderly patients after biliary surgery. Total clearance was 138.6±17.7 ml/min when 2.0 g was given as an i.v. bolus injection. The half-life of the β-phase averaged 110 min. The total clearance and the half-life of azlocillin were influenced by slight impairment of renal function (creatinine clearance 59.4±13.6 ml/min). In patients with normal liver function biliary excretion of the drug amounted to 5.3±2.8% of the dose (n=3) and the kinetics of biliary excretion were linear. In contrast, in two patients with impaired liver function biliary excretion was 0.2% and 0.5% of the dose, and kinetic analysis of biliary excretion rates revealed at least one zero order step in the excretion process. Renal excretion of the drug amounted to 45.0±17.7% of the dose, which means that 50% of the total clearance of azlocillin has to be accounted for by metabolic clearance.
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  • 68
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 23 (1982), S. 529-533 
    ISSN: 1432-1041
    Schlagwort(e): beta-blocker ; bufuralol ; enantiomers ; kinetics ; metabolism ; man
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary Single oral doses of (+)-, (−)- and (±)-bufuralol were administered to a healthy volunteer to compare the disposition and metabolism of the individual isomers and the racemate. Plasma levels and area under plasma curve (AUC) of the active isomer, (−)-bufuralol, were higher than those of the (+)-isomer; plasma clearance was correspondingly lower. Intermediate values were found for the racemate. The elimination half-life of (−)-bufuralol was shorter than that of (+)-bufuralol, but similar to the racemate. Both isomers were cleared almost entirely by metabolism. The main metabolic pathway for (−)-bufuralol was aromatic hydroxylation, whereas the principal route for (+)-bufuralol was conjugation. Phenol metabolites in the systemic circulation were present mainly as conjugates. Both isomers also underwent aliphatic hydroxylation. This pathway was more favoured by the (+)-isomer, although plasma levels and AUC of the principal product, 2′-hydroxy-bufuralol, were almost identical for the two forms. Major differences in metabolic fate thus had relatively little effect on the disposition of pharmacologically active metabolites.
    Materialart: Digitale Medien
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  • 69
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 24 (1983), S. 243-246 
    ISSN: 1432-1041
    Schlagwort(e): tolbutamide ; valproate ; intoxication ; activated charcoal ; inhibition of absorption ; sulphonylureas ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary The claim that activated charcoal should be ineffective or even contraindicated in intoxication due to tolbutamide is based only on limited in vitro studies. To test the claim, the effect of activated charcoal 50 g on the absorption of tolbutamide and, as a reference, of sodium valproate, was studied in 6 healthy volunteers. Each volunteer swallowed tolbutamide 500 mg and sodium valproate 300 mg with 50 ml water 1 h after a light breakfast, and within 5 min they took in randomized order either a suspension of activated charcoal or water. The absorption of tolbutamide, calculated as the peak concentration and the area under the serum drug concentration-time curve during 0–48 h, was reduced by 90% by charcoal (p〈0.001). The absorption of valproate in these conditions was reduced on average by 65% (p〈0.01). In each subject charcoal had a greater effect on the absorption of tolbutamide than of valproate. According to these findings and preliminary in vitro studies on other sulphonylureas high doses of activated charcoal can be recommended for the preventing the absorption of sulphonylureas in acute intoxications. The poor aqueous solubility of these substances at the gastric pH probably delays their gastrointestinal absorption, so that they may be adsorbed on to charcoal even given several hours later.
    Materialart: Digitale Medien
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  • 70
    Digitale Medien
    Digitale Medien
    Springer
    European journal of clinical pharmacology 22 (1982), S. 27-32 
    ISSN: 1432-1041
    Schlagwort(e): sulfonylureas ; diabetes ; chlorpropamide ; glipizide ; C-peptide ; insulin ; blood glucose ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary The influence of sulfonylurea on the secretion, disposal and effect of insulin was studied in 9 Type 2 diabetics during 3 one-month courses of treatment with a) chlorpropamide (t1/2〉24 h) once daily, b) glipizide (t1/2=2–4 h) once daily, and c) glipizide in divided doses. Food intake by each patient was identical during each period. Blood concentrations of immunoreactive insulin (IRI) and C-peptide (radioimmunoassays), and of glucose (enzymatic assay), chlorpropamide (gas chromatography) and glipizide (high-pressure liquid chromatography) were determined before and after breakfast and lunch on the 4th day of each examination period. All comparisons were intraindividual. Despite the lunch-time dose of glipizide given during the divided dose treatment, once-daily administration of this drug led to higher drug concentrations not only after breakfast but also for the first few hours after lunch. Divided dosage, on the other hand, led to higher concentrations later. In contrast to once-daily dosage, continuous exposure to glipizide was found in most patients. Chlorpropamide gave the most continuous sulfonylurea exposure. The blood glucose levels were inversely related to the concurrent sulfonylurea concentrations; glucose levels after breakfast and lunch were lowest during once-daily glipizide, whereas the fasting level was lowest during chlorpropamide treatment. The IRI response to breakfast was 60%–70% higher during once-daily glipizide than during the other two treatments, but the C-peptide responses to breakfast were almost identical. Thus, the greater after-breakfast availability of peripheral insulin appeared to be due to an effect of glipizide on the extrapancreatic disposal of the hormone.
    Materialart: Digitale Medien
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  • 71
    ISSN: 1432-1041
    Schlagwort(e): digoxin ; verapamil ; digoxin-verapamil interaction ; kinetics ; plasma level ; renal clearance ; extra-renal clearance
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie , Medizin
    Notizen: Summary Single-dose investigations in healthy subjects have demonstrated substantial impairment of renal and extrarenal clearance of digoxin during coadministration of verapamil. A longitudinal study has been performed to assess the changes in digoxin disposition during long-term verapamil therapy. After one week of verapamil 240 mg/d mean plasma digoxin had risen from 0.21±0.01 ng/ml (SE) to 0.34±0.01 ng/ml (p〈0.01), and renal digoxin clearance had fallen from 197.57±17.37 ml/min to 128.20±10.33 ml/min (p〈0.001). These changes gradually subsided, and after six weeks, renal digoxin clearance had normalized and plasma digoxin had declined to 0.27±0.02 ng/ml (NS). The 24-h urinary recovery of digoxin increased from 46.46±3.23% before to 69.78±3.69% (p〈0.001) after six weeks of verapamil co-administration, and this elevation persisted throughout the study. The verapamil-induced suppression of renal digoxin elimination disappears over a few weeks of drug exposure, whereas the inhibition of the extrarenal clearance of digoxin seems to persist.
    Materialart: Digitale Medien
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  • 72
    ISSN: 1432-072X
    Schlagwort(e): Key words Auxostat ; Batch culture ; Chemostat ; Continuous culture ; Fermentation control ; Inhibition ; kinetics ; Nutristat ; On-line measurement ; Pentachlorophenol ; Pollutant ; Sphingomonas ; Steady-state conditions ; Toxicity
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Biologie
    Notizen: Abstract A bacterium degrading pentachlorophenol (PCP) as the only source of carbon and energy was grown in a “nutristat”, i.e., a continuous culture with on-line measurement and control of the substrate concentration. We improved the PCP nutristat by incorporation of a personal computer with a proportional integral derivative (PID) algorithm for controlling the medium feed pump. The controlled value deviated from the average (set-point) value by 1% maximally. In the PCP nutristat (30°C), the steady-state dilution rate, and hence, specific growth rate, showed a maximum value of 0.142 ± 0.004 h–1 at set-point PCP concentrations between 37 and 168 μM. At PCP concentrations above 168 μM, the steady-state growth rate decreased because of inhibition. The growth yield coefficient was not seriously affected by the PCP concentration, suggesting that uncoupling was not the inhibitory mechanism. It was concluded that the PCP nutristat is very useful for establishing steady-state conditions that maintain growth-inhibitory PCP concentrations and high cell concentrations, conditions for which the chemostat is not suitable.
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  • 73
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 47 (1996), S. 35-49 
    ISSN: 1572-8943
    Schlagwort(e): bone cement ; DSC ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Bone cements are widely used for the fixation of metallic prostheses in orthopaedics and to form replacements for skull defects in neurosurgery. Acrylic bone cements are based on a mixture of methyl methacrylate (MMA) and a fine powder of polymethyl methacrylate (PMMA). The polymerization of the bone cement occurs in contact with the bone and the prosthesis which act as the boundaries of a bulk polymerization reactor. The kinetic behaviour of the bone cement plays a fundamental role for the final performance of the implant. In this paper, the isothermal and non-isothermal polymerization behaviour of a commercial bone cement is described. A simple phenomenological model, accounting for the autoacceleration ffect, for a diffusion controlled termination mechanism and for the reaction between inhibitor and initiator, is proposed. The reaction kinetics is analysed by DSC. DSC data are used for the determination of the rates of polymerization under isothermal and non-isothermal conditions. The experimental data are processed to calculate the parameters of the proposed phenomenological kinetic model. The analytical and numerical details related to the integration of the model are discussed.
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  • 74
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 47 (1996), S. 543-557 
    ISSN: 1572-8943
    Schlagwort(e): compensation effect ; DSC ; kinetics ; TG
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Four computer programs as well as one demo-version for non-linear evaluation of kinetic data in thermal analysis and calorimetry, were presented. The multi-task program TA-kin meets all mathematical requirements for solving the numerical assignments. It is shown that the so-called compensation effect is due to the mathematical structure of the Arrhenius equation. Several applications of TA-kin to a lot of DSC- and TG-measurements and isoperibolic batch experiments as well as adiabatic semi batch experiments realized by precision calorimetry have been discussed.
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  • 75
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 47 (1996), S. 569-575 
    ISSN: 1572-8943
    Schlagwort(e): Bi2O3 ; CaCO3 decomposition ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Former studies concerning the formation of the compounds in the pseudobinary systems of Bi2O3-MO type (M =Ca, Sr, Ca+Sr) have shown that the reaction which occurs with the highest rate is that between Bi2O3 and CaO. In the present work CaCO3 was used as CaO source. We carried out an investigation of the thermal decomposition of CaCO3 in the presence of Bi2O3 in comparison with the decomposition of pure CaCO3. The presence of Bi2O3 exerts a complex influence on the CaCO3 decomposition acting on the nucleation as well as on the diffusion of CO2. The decomposition of the samples with low Bi2O3 content follows the mechanism of a contracting sphere. A change from surface nucleation to bulk nucleation is recorded for higher amounts of Bi2O3.
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  • 76
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 47 (1996), S. 1437-1450 
    ISSN: 1572-8943
    Schlagwort(e): browning ; crystallization ; glass transition ; kinetics ; milk powder ; water
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract An exotherm, observed in differential scanning calorimetry (DSC) scans of amorphous food materials above their glass transition temperature,T g, may occur due to sugar crystallization, nonenzymatic browning, or both. In the present study, this exothermal phenomenon in initially anhydrous skim milk and lactose-hydrolyzed skim milk was considered to occur due to browning during isothermal holding at various temperatures above the initialT g. The nonenzymatic, Maillard browning reaction produces water that in amorphous foods, may plasticize the material and reduceT g. The assumption was that quantification of formation of water from theT g depression, which should not be observed as a result of crystallization under anhydrous conditions, can be used to determine kinetics of the nonenzymatic browning reaction. The formation of water was found to be substantial, and the amount formed could be quantified from theT g measured after isothermal treatment at various temperatures using DSC. The rate of water formation followed zero-order kinetics, and its temperature dependence well aboveT g was Arrhenius-type. Although water plasticization of the material occurred during the reaction, and there was a dynamic change in the temperature differenceT−T g, the browning reaction was probably diffusioncontrolled in anhydrous skim milk in the vicinity of theT g of lactose. This could be observed from a significant increase in activation energy. The kinetics and temperature dependence of the Maillard reaction in skim milk and lactose-hydrolyzed skim milk were of similar type well above the initialT g. The difference in temperature dependence in theT g region of lactose, but above that of lactose-hydrolyzed skim milk, became significant, as the rate in skim milk, but not in lactose-hydrolyzed skim milk, became diffusion-controlled. The results showed that rates of diffusion-controlled reactions may follow the Williams-Landel-Ferry (WLF) equation, as kinetic restrictions become apparent within amorphous materials in reactions exhibiting high rates at the same temperature under non-diffusion-controlled conditions.
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  • 77
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 48 (1997), S. 917-923 
    ISSN: 1572-8943
    Schlagwort(e): copper compound ; coupled technique ; kinetics ; macrocyclic complex ; non-isothermal
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The thermal decomposition process of the complex [Cu(NBOCTB)][Cu(NO3)4] H2O has been studied by TG and DTG technique, and possible intermediates of the thermal decomposition have also been conjectured from the TG and DTG curves. The results suggest that the decomposition of the complex involves five steps: The non-isothermal kinetics of steps 1, 2 and 3 have been studied by means of the Achar and Coats-Redfern method based on TG and DTG curves. Step 1 is a ‘Coring and Growth’ mechanism (n= 1), its kinetic equation may be expressed as: dα/dt=Ae−E/RT(1−α). Steps 2 and 3 are both ‘two order chemical reaction’ mechanisms, their kinetic equations can be expressed as: dα/dt=Ae−E/RT(1−α)2.
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  • 78
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 49 (1997), S. 87-94 
    ISSN: 1572-8943
    Schlagwort(e): kinetics ; poly(di-propyl itaconates) ; polymer structure ; thermal degradation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Non-isothermal thermogravimetry was performed in a dynamic nitrogen atmosphere, on a series of poly(di-n-propyl itaconates) (PDnPI) and poly(di-iso-propyl itaconates) (PDiPI) which had been prepared in the presence of various amounts of the chain transfer agentn-dodecyl mercaptan (DDM). Differential thermogravimetry (DTG) showed that both polymers degraded in two stages. The DTG curve of PDnPI had a large first peak followed by a smaller shoulder, whereas the DTG curve of PDiPI was composed of two peaks of almost equal heights. The addition of DDM during the polymerisations in both cases resulted in a similar decrease in the relative area of the first peak.
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  • 79
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 49 (1997), S. 183-191 
    ISSN: 1572-8943
    Schlagwort(e): kinetics ; thermooxidative degradation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The results of non-isothermal kinetic analysis of the thermooxidative degradation in air and oxygen of an unsaturated polyester resin are presented. It has been shown that the thermooxidative degradation in oxygen occurs at lower temperatures than the thermooxidative degradation in air. The kinetic parameters of the thermooxidative degradation depend on the heating rate and the oxygen pressure. Two straight lines of InAvs. E (A is the preexponential factor andE is the activation energy), characteristic for the compensation effect, have been obtained for the thermooxidative degradation in air and in oxygen respectively. The difference between the intercepts of these straight lines can be explained by dependence of the pre-exponential factor on the oxygen pressure.
    Materialart: Digitale Medien
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  • 80
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 46 (1996), S. 795-808 
    ISSN: 1572-8943
    Schlagwort(e): DSC ; kinetics ; liquid crystalline polymer ; optical transmittance ; polycarbosilane ; side-chain mesogen ; transition parameters
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract This paper is concerned with an analysis of the thermodynamics and kinetics of mesophase formation by cooling from the isotropic state of side-chain liquid crystalline polycarbosilanes containing spacers in the range from 3 to 11 CH2-groups. The polymers are characterized by their thermotropic behaviour as far as temperature, enthalpy and entropy of the transitions are concerned. The kinetics was followed by optical and calorimetric methods. Longer spacer length leads to more perfect ordering in the mesophase, higher isotropization temperatures, and lower glass transition temperatures. The Avrami and Ozawa formalism to describe the transition kinetics to the mesophase from the isotropic state cannot be interpreted as the nucleation and growth mechanism known from crystallization.
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  • 81
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 49 (1997), S. 857-862 
    ISSN: 1572-8943
    Schlagwort(e): analytical methods ; kinetics ; powder milk ; temperature
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract This work present comparative results on powder milk storage quality, obtained from analytical methods. Protein content was determined conventional (Kjeldahl) and colorimetric with biuret reagent at 540 nm and integral quality by thermogravimetric and biological methods. A method was developed for the protein separation of powder milk. Powder milk was submitted to degradation processes at 45, 60 and 80°C for 20 days. The results indicated that protein content values were inconsistent if determinations by Kjeldahl and colorimetric methods and biological tests were compared. There is evidence of thermal decomposition of powder milk as detected by biological and thermogravimetric methods.
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  • 82
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 49 (1997), S. 937-941 
    ISSN: 1572-8943
    Schlagwort(e): kinetics ; mebendazole ; quality control ; technology
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A study was made of the thermal behavior of the starting materials, their mixtures and the resulting mebendazole tablets. The thermal curves were obtained with a Shimadzu thermobalance, model TGA-50, using an air flow of 50 mL min−1 and a heating rate of 10°C min−1 in the temperature interval 30–900°C. The reaction constant velocities for the mebendazole salt and tablets were determined isothermally, using the Arrhenius expression. The thermal stability of mebendazole tablets is lower than that of the mebendazole salt, due to the presence of starch and lactose in the composition. Analysis of the data reveals that thermogravimetry is a powerful tool in pharmaceutical technology and quality control.
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  • 83
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 47 (1996), S. 1081-1091 
    ISSN: 1572-8943
    Schlagwort(e): kinetics ; thermal degradation
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The kinetic study of thermal degradation takes into account the validity of the Arrhenius equation. From TG data, the activation energy,E a and pre-exponential factor,A, are evaluated. These results are interpreted by using the ‘kinetic compensation effect’ as basis. A linear correlation between In(A) andE a is obtained in all cases studied. However, in a plot of the logarithm of the rate constant as a function of reciprocal temperature for the same series of reactions, the thermal oxidative degradations of Nylon-6 and PVC display a point of concurrence and one isokinetic temperature, whereas those of HIPS and PC do not. Therefore, in the thermal oxidative degradations of Nylon-6 and PVC a ‘true’ compensation effect occurs, which could be related to the bulk properties of metal oxides, such as different valence states, whereas for other polymers it displays only an ‘apparent’ compensation effect. This means that degradation is largely independent of the bulk properties of oxides, but may be related to the distribution of different kinds of active links in the polymer surface having different activation energies.
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  • 84
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 48 (1997), S. 343-348 
    ISSN: 1572-8943
    Schlagwort(e): activation energy ; combustion ; crude oil ; differential scanning calorimetry ; kinetics ; thermogravimetric analysis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A weighted mean activation energy method was applied to describe the reactivity and combustibility of crude oils via simultaneous TG/DTG. Thermal experiments were conducted with a non-isothermal method at a heating rate of 10
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  • 85
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 48 (1997), S. 385-401 
    ISSN: 1572-8943
    Schlagwort(e): dehydration and decomposition ; kinetics ; Fe(III) chloride
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Fe(III) chloride hydrate (FeCl3·xH2O) undergoes simultaneous dehydration and dehydrochlorination from its molten phase in the temperature range 100–200
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  • 86
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 48 (1997), S. 413-425 
    ISSN: 1572-8943
    Schlagwort(e): alcoholic fermentation ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The control of alcoholic fermentation is necessary to obtain a quality wine. The overall dynamic and phenomenological modelling already applied to the simulation of this type of reaction enables us to suggest, in this study, a simple model (of which two variants), are relatively satisfactory. The first variant does not take into account the variation of the ambient temperature; the model translates exactly the first phase of the experimental curve or the moment when highest temperatures are measured. The relaxation phase is less well described because of influence of variation of the ambient temperature is relatively important. The second one considers the system depending on the ambient temperature, the model is correct for the relaxation phase too (the reaction temperature decreases, it nears the ambient temperature). The advantage of this model: It permits one to determine the reaction enthalpy and the kinetic parameters.
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  • 87
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 48 (1997), S. 623-634 
    ISSN: 1572-8943
    Schlagwort(e): bismalleimide/carbon fiber composite ; DMA ; kinetics ; TSC
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The correlation between structure/microstructure and thermomechanical properties has been investigated by the Thermally Stimulated Creep (TSC) technique in a high performance thermostable thermoset matrix composite. The high resolving power of this technique allows us to analyse the α retardation mode. The kinetics of molecular movements liberated at the glass transition has been investigated by the technique of fractional loading: the analysis of each elementary process gives the real compliance and the retardation time as a function of temperature. The values of the activation parameters show the existence of a compensation phenomenon which characterizes the microstructure. It also gives access to the loss compliance of the composite material as a function of temperature and frequency. The predictive calculation of loss compliance has been validated by the results obtained by dynamic mechanical analysis (DMA).
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  • 88
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 48 (1997), S. 769-782 
    ISSN: 1572-8943
    Schlagwort(e): kinetics ; non-linear optimization ; reactor time constants ; software ; time constants of sensors
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract All temperature sensors have a finitely time constant. The influence of the sensor time constant gts on the results of kinetic evaluation is demonstrated at four reaction types. The ignorance of the sensor indolence gives incorrect activation parameters. Therefore the determination of Τs is necessary. For the estimation of parameters the nonlinear evaluation program TA-kin was used. With its help it is possible to find the real parameters, also when Τs=32 s, if the real Τs-value was entered.
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  • 89
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 49 (1997), S. 1517-1525 
    ISSN: 1572-8943
    Schlagwort(e): β-cyclodextrin ; cinnamyl alcohol ; kinetics ; thermal analysis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The stability of β-cyclodextrin-cinnamyl alcohol inclusion complex (β-CD·C9H10·8H2O) was investigated using TG and DSC. The mass loss took place in three stages: the dehydration occurred between 50–120°C; the dissociation of β-CD·C9H10O occurred in the range of 210–260°C; and the decomposition of β-CD began at 280°C. The dissociation of β-CD·C9H10O was studied by means of thermogravimetry, and the results showed: the dissociation of β-CD·C9H10O was dominated by a two-dimensional diffusion process (D2). The activation energyE was 161.2 kJ mol−1, the pre-exponential factorA was 4.5×1013 min−1. Cyclodextrin is able to form inclusion complexes with a great variety of guest molecules, and the interesting of studies focussed on the energy binding cyclodextrin and the guest molecule. In this paper, β-cyclodextrin-cinnamyl alcohol inclusion complex was studied by fluorescence spectrophotometry and infrared absorption spectroscopy, and the results show: the stable energy of inclusion complexes of β-CD with weakly polar guest molecules consists mainly of Van der Waals interaction.
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  • 90
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 49 (1997), S. 1553-1564 
    ISSN: 1572-8943
    Schlagwort(e): deconvolution ; differential scanning calorimetry ; feedforward neural networks ; kinetics ; signal filtering ; simulations ; thermal analysis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Feedforward neural networks have been used for kinetic parameters determination and signal filtering in differential scanning calorimetry. The proper learning function was chosen and the network topology was optimized, using an empiric procedure. The learning process was achieved using simulated thermoanalytical curves. The resilient-propagation algorithm have led to the best minimization of the error computed over all the patterns. Relative errors on the thermodynamic and kinetic parameters were evaluated and compared to those obtained with the usual thermal analysis methods (single scan methods). The errors are much lower, especially in presence of noisy signals. Then, our program was adapted to simulate thermal effects with known thermodynamic and kinetic parameters, generated electrically, using a PC computer and an electronic interface on the serial port. These thermal effects have been generated by using an inconel thread.
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  • 91
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 49 (1997), S. 1467-1475 
    ISSN: 1572-8943
    Schlagwort(e): CRTA ; DSC ; kinetics ; synthetic brochantite ; TG-DTA ; thermal decomposition
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The reaction pathway of the thermal decomposition of synthetic brochantite, Cu4(OH)6SO4, to copper(II) oxide was investigated through the detailed kinetic characterization of the thermal dehydration and desulferation processes. The dehydration process was characterized by dividing into two overlapped kinetic processes with a possible formation of an intermediate compound, Cu4O(OH)4SO4. The dehydrated sample, Cu4O3SO4, was found first to be amorphous by means of XRD, followed by the crystallization to a mixture of CuO and CuO-CuSO4 at around 776 K. The specific surface area and the crystallization behaviour of the amorphous dehydrated compound depend largely on the dehydration conditions. The thermal desulferation process is influenced by the gross diffusion of the gaseous product SO3, which is governed by the advancement of the overall reaction interface from the top surface of the sample particle assemblage to the bottom.
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  • 92
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 50 (1997), S. 455-462 
    ISSN: 1572-8943
    Schlagwort(e): kinetics ; statistical analysis
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A statistical technique based on the Wilcockson criterion is suggested for estimation of the reproducibility of thermoanalytical experiments. Reduction of the whole physicochemical process to a quasi-one-stage process is described.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 93
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 50 (1997), S. 425-430 
    ISSN: 1572-8943
    Schlagwort(e): decomposition ; kinetics ; non-isothermal
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The authors present the results concerning the thermal behaviour of three polynuclear coordination compounds of Nd(III) and Co(II) or Fe(III) with triptophan. For the dehydration steps the values of the non-isothermal kinetic parameters have been determined.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 94
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 52 (1998), S. 569-579 
    ISSN: 1572-8943
    Schlagwort(e): bromomethylated polysulfone ; carboxylated polysulfone ; kinetics ; polysulfone ; thermoxidative decomposition
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Kinetic aspects of the first step of thermoxidative decomposition, under dynamic conditions of heating, of some polysulfones have been studied. The dependence of the kinetic parameters on the heating rate and conversion degree has been established. The compensation effect and conversion function have also been discussed. Polysulfone decomposes by the breaking of the main chain, a process involving very high activation energy. Chemically modified polysulfones show the first step of thermoxidative decomposition at relatively low temperatures. This step corresponds to the elimination of functional side - groups for the bromomethylated polysulfone while in the case of the carboxylated polysolfone, the loss of the carboxyl group is probably accompanied by a crosslinking reaction.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 95
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 53 (1998), S. 397-410 
    ISSN: 1572-8943
    Schlagwort(e): barium oxalate ; kinetics ; non-isothermal thermogravimetry ; stepwise isothermal analysis ; thermal decomposition
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Thermal decomposition of BaC2O4·0.5H2O in air was studied by a combination of stepwise isothermal analysis (SIA) and non-isothermal thermogravimetry. The results from both techniques show that the crystal water is released in one step and that anhydrous barium oxalate is decomposed in one step, while BaCO3 decomposes in three steps to BaO, forming two intermediate compounds with the formulas of BaCO3·(BaO)2 and (BaCO3)0.5·(BaO)2.5. Reaction mechanism analyses using the data from SIA measurements show that the controlling mechanism for all the five decomposition steps in isothermal conditions is a two-dimensional phase-boundary controlled process. Kinetic parameters are obtained for the five decomposition steps from the non-isothermal thermogravimetric data.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 96
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 54 (1998), S. 695-704 
    ISSN: 1572-8943
    Schlagwort(e): activation energy ; decomposition ; kinetics ; modulated temperature ; thermogravimetry ; volatilization
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract A new technique, called modulated thermogravimetry, is introduced as a tool for obtaining continuous kinetic information for decomposition and volatilization reactions. The approach makes use of an oscillatory temperature program to obtain kinetic parameters during a mass loss. MTGA™ may be used under quasi-isothermal conditions to observe a single mass loss or may be combined with linear heating rate or Hi-Res™ controlled rate thermogravimetry to scan from one mass loss region to another. Results obtained are in agreement with those obtained by other kinetic methods.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 97
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 54 (1998), S. 947-956 
    ISSN: 1572-8943
    Schlagwort(e): β-cyclodextrin ; ethyl benzoate ; inclusion complex ; kinetics ; thermal decomposition
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The stability of β-cyclodextrin·ethyl benzoate·6H2O(β-CD·C6H5COOC2H5·6H2O) was investigated by TG and DSC. The mass loss takes place in three stages: the dehydration occurs at 50-120°C; the dissociation of β-CD·C6H5COOC2H5occurs at 200-260°C; the decomposition of β-CD begins at 280°C. The kinetics of the dissociation of β-CD·C6H5COOC2H5in a dry nitrogen flow was studied by means of thermogravimetry both at constant temperature and linearly increasing temperature. The results show that the dissociation of β-CD·C6H5COOC2H5is dominated by a three-dimensional diffusion process (D3). The activation energy E is 116.19 kJ mol-1and the pre-exponential factor A 6.5358·109min-1. Cyclodextrin is able to form inclusion complexes with a great variety of guest molecules, and the studies focus on the energy of binding between cyclodextrin and the guest molecule. In this paper, the β-cyclodextrin·ethyl benzoate inclusion complex was studied by fluorescence spectrophotometry and infrared absorption spectroscopy, and the results show that the stable energy of inclusion complexes of β-CD with weakly polar guest molecules consists mainly of van der Waals interaction.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 98
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 55 (1999), S. 9-19 
    ISSN: 1572-8943
    Schlagwort(e): ARC ; DSC ; HFC ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract Isopropylnitrate (IPN) is described as a detonable material used in propellants and explosives. While there is considerable information available on its sensitivity and compatibility with other materials, very little is known about its thermochemical properties. This paper will describe the results obtained from some DSC, heat flux calorimetry (HFC) and accelerating rate calorimetry (ARC) measurements. The ASTM DSC method using a hermetic aluminum pan having a lid with a laser-produced pin hole was used to determine the vapour pressure of IPN1. Results calculated from an Antoine equation are in substantial agreement with those determined from DSC measurements. From the latter measurements, the enthalpy of vaporization was determined to be 35.32±0.62 kJ mol−1. Attempts to determine vapour pressures above about 0.8 MPa resulted in significant decomposition of IPNg. The enthalpy change for decomposition in sealed glass systems was found to be -3.43±0.09 kJ g−1 and -3.85±0.03 kJ g−1, respectively from DSC and HFC measurements on IPN1 samples loaded in air. Slightly larger exotherms were observed for the HFC results in air than those in inert gas, suggesting some oxidation occurs. In contrast, no significant difference in the observed onset temperature of about 150°C was observed for both the HFC and ARC results. From DSC measurements, an Arrhenius activation energy for decomposition of 126±4 kJ mol−1 was found. These measurements were also conducted in sealed glass systems and decomposition appeared to proceed primarily from the liquid phase.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 99
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 55 (1999), S. 233-241 
    ISSN: 1572-8943
    Schlagwort(e): cadmium(II) atom ; kinetics ; non-isothermal decomposition ; Schiff-base compound
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The crystal C81H78N12O6Cd3 was synthesized and its structure was determined by single crystal X-ray diffraction method. The complex crystallizes in the monoclinic system space group P21/n with cell parameters, a=15.959(4) Å, b=26.222(3) Å, c=25.907(6) Å, β=101.60(2)°. The non-isothermal kinetics of the crystal was studied by use of non-isothermal TG and DTG curves. The kinetic parameters were analyzed by means of integral and differential methods, and mechanism functions of the thermal decomposition reaction for its second step were proposed. The kinetic equation of thermal decomposition is expressed as: dα/dt=Aexp(-E/RT)1.5(1-α)4/3[1/(1-α)1/3-1]−1. The average values of E(kJ mol−1) and lnA/s−1 are 339.25, 43.95, respectively.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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  • 100
    Digitale Medien
    Digitale Medien
    Springer
    Journal of thermal analysis and calorimetry 55 (1999), S. 301-309 
    ISSN: 1572-8943
    Schlagwort(e): dehydroxylation ; goethite ; kinetics
    Quelle: Springer Online Journal Archives 1860-2000
    Thema: Chemie und Pharmazie
    Notizen: Abstract The kinetics of thermal dehydroxylation of aluminuous goethites [1] synthesised from a ferrous salt has been re-examined using the general reaction order kinetic law. The utilised data processing was based on the procedures employed by dissolution kinetics. Recalculation of the activation energies EA of the dehydroxylation yielded the values 130, 132, 128, and 123 kJ mol−1 for pure goethite, goethite with 10, 20, and 30 mol% Al substitution, respectively. The values of EA are in a good agreement with those given for goethite in literature. The EA values are linearly related with the chemically bound excess H2O/OH− in the crystal lattice that is apparently influenced by Al substitution.
    Materialart: Digitale Medien
    Standort Signatur Erwartet Verfügbarkeit
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